Ureide of dialkyl-acetic and process of making same.



. e m t... M Boo "UNITED STATES;

Patented October 25, 1904.

PATENT OFFICE.

IEMIL FISCHER, OF BERLIN, ANDJOSEF VON MERING, OF HALLE-ON-THE- SAALE, GERMANYJASSIGNORS TO THE FIRM OF E. MERGK, or DARM-j STADT, GERMANY.

i UREIDE OF DIALKYL-ACETIC ACID AND PROCESS OF MAKING SAME.

SHBCIFICATION forming part of- Letters Patent No. 773,251, dated October 22s, 1904.

I Application filed larch 9, 1903.

To all whom it may concern:

Be it knownthat we, EMIL FISCHER, residing at Hessischestrasse 2, Berlin, and Jose! VON MERrNo, residing at Halle-on-the-Saale, Germany,-subjects of the German Emperor, have invented certain new and useful Improvements in Ureides of Dialkyl-Acetic Acids and Processes for thePreparation of Such,of. which the following scription.

The subject of this invention is a group of I hitherto unknown chemical compounds-40 wit, ureides of dialkyl acetic acids, also called dialkyl-a'cetyl ureasand a process .for preparing such compounds. q

Malonic acid may be combined with urea by the action of phosphorus oxychlorid, so as to formbarbituric -acid. (Grimaux, Bulletin Soc. Claim. (Z4; Parts, 31, 14:6.) .Thesame process is applicable: to the therein so called iiimethyl-malonic acid. (-Thorne, Journal of t/z-O/mnical Societgz, 39, 545.). .'Experiments made by us have shown that when op: erating under similar conditions with those derivatives of malonic acid which contain two ethyls, two propyls, or other (like or unlike) I .alkyls rich in carbon the formation of a barbituric acid does not take place at all or only in a very imperfect degree and that a different action takes place, which results in'the formation o'f hitherto unknown -ureides of is aclear, full, andexact dedialkyl-acetic acids--that is, dialkylacetyl The processshown in this particular example consists in condensing a dialkyl-malonic acid with urea, so'as to split off both carbon dioxid and water. .-The remainder is the dialkyl-acetyl urea thus'ne'w ly formed. This Serial No. 146,355. (Specimens) operationban be performed in onestep, as above stated and shown, or it can be done in two successive steps, as will he showu'further,

below. 'Emmgiles of Cohdewsatz'on. i i One Step. N0'i'E.-The word parts, hereinafterused to denote proportions in which ingredients or components'are mixed or employed, is

and 25.6 partsof phosphorus oxychlorid are added to the mixture, an energetic reaction takes place with etfervescence, lVhen that has ceased,- heat is applied for several hours on the water-bath. The mass-aftercooling is extracted with asmall quantity of cold water,

which leaves undissolved the new product, which is collected on a filter and crystallized from hot water. ltscomposition is 01H N202,

and it melts at 207.5 centigrade, (corn) Itdissolves in about one hundred and twenty parts of hot water and crystallizes in the form of line needles. 'In hot alcohol it is much more freely soluble. its composition is demonstrated by its reaction with concentratedv hydrochloric acid at 1OO 'centigrade, when. it yields urea and diethyl-acetic acid. In

carrying out the process indicated above the needed proportion of phosphorus oxychlorid may be'.considerably reduced by. first mixing carefullyfifty parts ofdiethyl-malonic acid and 18.6 parts of urea, preferably by meltihg them together under diminished pressure at about 110 centigrade. The whole is then cooled down to about centigrade, and sixteen parts of phosphorus oxychlorid are added. in successive portions, the mixture meanwhile being well stirred. It is then heated for about an hour on the water-bathj The resulting mass when cold is treated with spontaneously to deposit by cooling. A pure like manner.

equivalentquantity of dipropyl malonic acid,

"chlorid are added and after the reaction has subsided the mass, is heated for eight to ten 178.5- centigrade, (corn) 1t dissolves-in 4o then boiled with alcohoL-which leaves undis- -lts composition is represented by the fora little cold water, and the residue boiled with about twenty-five times its "bulk of water, the methyl-ethyl-acetyl urea passes into solul cold water, and the undissolved residue is solved only a comparatively small portion thereof, whereupon the diethyl-acetyl urea contained in the alcoholic solution is allowed preparation is obtained by redissolving in hot water. The phosphorus oxychlorid used in this process may be replaced .by phosphorus trichlorid, phosphorus pentachlorid thionyl chlorid, sulfnryl chlorid, acetyl chlori'd, chlor sulfonic acid, or other acid chlorids acting in 2. Diprwyl-acetyl -w/"i:(/,.-Whcn in theprocess described in Example 1 the diethyl- 'malonic acid is replacedby the molecularly analogous results-areobtained. The product is, however, so sparingly soluble in water as to require recrystallization from hot alcohol.

mula: CeHuN2O2. It melts at192.5 centigrade (corn) and crystallizes from the alcoholic solution in fine colorless needles. It requires about five hundred parts of hot water for complete solution.

3. Miefliylcthyl-acetyl wee. When to a' .m'xture oi twenty parts of powdered methylethyl-malonic acid and twenty parts of powdered urea sixteen parts of phosphorus oxyhours on the water-bath, then extracted-with tion and is deposited, as the solution cools, in the form of colorless needles melting at about twenty-six parts of hot water, and its composition is represented by the formula: CoHwNzOz. i

Examples 0 (/bn-llcnsutimzin Two St .9.

and in the second stage the urcido-dialkylmalonic and so formed is split up into carfuming sulfuric acid as a condensing agent:

4/ DZeth I Z-avet Z u-rea.A carefully-prepared mixture of two parts of diethyl-malonic acid and one part of ureais added to four parts of' fuming sulfuric acid conoughly cooled by a freezing mixture of salt and ice. If on removal ofithe freezin mixture the thick pasty mass under reaction becomes hot, this heating must be'moderated by againapplying cooling agents. Otherwise sulting in the charring of theorganic substance. When this spontan eous cheating ceases to be noticeable, the mass is heated on the water-bath for fa sho'rt period, during five times its weight of cold water. "The c'rystalli ne mass resulting hQIBQII IS separated-by filtration and redissolved inhotwater. In

ethyl-malonic acid-'are obtained, which are freely soluble in alkalis, but very sparingly so in cold water. At 162 centigradethis acid begins to be converted into diethylacetyl urea, withviolent evolution of car- .bonic acid. In order to obtain pure diethylacetyl urea, all. that isreguisite is to recrystallizefrom hot water the solid residue obacid to 165 to 170 centi'grade.

malonic acid. :On treating such intermediate 7, product, however, with dilutealksline' solutions theureido-dipropyl-malonic acid goes dition of acids be precipitated in the form of a white crystalline mass. The latter has the composition correspondingto CwHaOiNz and 'melts ata temperature of 146. centigrade, at the sametime giving '06 carbon dioxid and Dimethyl-malonic acid treated by the above steps reacts in a manner different from that of diethyl and dipropyl malonic acids. On its being mixed with urea and acted on by is formed.

It will be observed that each of theureides claimed herein answers tothe general formula (Alk)2CH.G O.NH.CO.NH2, in which (Alk): represents two alkyls of those specified as producing a ureide,. one zit-least of which alkyls has more than one carbon atom. Each of the ureidcs claimed is soluble in hot water honi acid and the corresponding dialkyland hot alcohol, isinsolublcin cold. potassium tained by heating the ureido-diethyl-inalonic being transformed into dipropyl-acetyl urea.

acetyl urea. This is effected by the use of taining seventy per cent..of anhydri'd, thor-' a very violent reaction might take place, re-v which seine bubbles ofga s are evolved. The cooled viscous mass is afterward poured into this way fine lustrous flakes ofureido-di- 5'. .Dr'xpropyl-acetyl urea.-In case dipro pyl-ma'lonic acid be used in the place of the diethyl malonic acid oi the foregoingexample the reaction takes, on thewhole, asjmilar turn." In this case the intermediate'product of the. first step .is" always a mixture 'dipropyl-acetyl urea and ureido dipi'opyl IOC into solution, from which it may by'the adfuming sulfuric acid dimethyl-barbituric acid or sodium hydrate solution, and is decomposable by hydrochloric acid at 100 Centigrade into urea and a diakyl-acetic acid.

We are aware that besides the variationsand modifications of process already indicated above others are possible, as well in the method sential nature of our invention.

. We are aware'that the general formula specified in claim 1 may represent other examples of the group of substances than those specifically described heretofore. We have included under the term dialkyl the diethyl, dipropyl, and methyl ethyl radicals; and it will be obvious that-the two alkyls may be the same or different.

We claim- 1. As a new composition of matter, a dialkyl-acetyl urea having the general formula (A1k).=oH.oo.NH;oo.NH., wherein (Alk)z represents two organic radicals, one at-least of which has more ,than'one carbon atom, said composition of matter be? mg soluble in hot water and hot alcohol, insoluble in cold potassium orsodium hydrate solution, and decomposable by hydrochloric acid at 100 centigrade into urea and a di alkyl-acetic acid. 4

2, Diethyl-acetyl urea having the formula Cal 114N202, which crystallizes from hotwater in the form of fine needles, melting at about 207 centigrade, and which is soluble in about one hundred and twenty parts of hot water, more freely soluble in hot alcohol, and which is decomposable by hydrochloric acid at 100v centigrade into urea and diethyl-acetic acid.

3. The process of preparing a ureide of a dialky l-acetic acid, which consists in acting on urea and a dialkyl malonic acid (at least one of the alkyls of which acid has more'than one carbon atom) simultaneously by a suitable condensing agent, which at least splits oil water;

and subsequently, if needed, applying heat to. split ofi carbon dioxid also and thus isolate the desired new product. Y

4. The process of preparing a ureide of a dialkyl-acetic acid, which consists in condensing urea and a dialkyl-malonic acid (at least one .lonic an acid has more than one carbon atom) by a suitof the alkyls of which acid has more than one carbon atom) into a new product 'hsgaeting on them simultaneously by a suitable acid chlorid, so as tosplit oil water and carbon dioxid.

5. The process of preparing a ureide of a dialkyl-acetic acid, which consists in condensing urea and a dialkyl-malonic acid (at least one of the alkyls of which acid has more than one carbon atom) into a new product by acting on them simultaneously by a suitable acid chlorid, so as to split ofi water and carbon dioxid, and then isolating the condensation product thus obtained.

6. The process of preparing a ureide of a {ll-- alkyl-acetic acid, which consists in condensing urea and a dialkylmalonic acid (at least one -bon dioxid; isolating the condensation product, and splitting'ofi carbon dioxi'd'therefrom through the application of heat:

7. The process of preparing azureide of adi- -alkyl-acetic acid (that is, preparing adiallcylacetyl urea), which consists in bringing about condensnation between urea and a dialkyl-ma- 1 (at least one of the'alkyls of which able condensing agent, so as to split off water and carbon dioxid therefrom.

8. The process of preparinga ureide of a dialkyl-acetic acid (that is, preparing a dialkylacetyl urea), which consists in bringing about condensation between-mea and adialkyl-malonic acid (at least one of the alkyls of which acid has more than one carbon atom) by a suitable condensing agent, so as to split off water and carbon dioxid therefrom, and then purifying the product of such condensation.

' 9. Theprocess of preparing a diethyl-acetyl urea, which'c hsists in bringing about condensation betwee nreaandadiethylalonic acid by a suitablefgondensing agent, s as tasplit oif water and carbon dioxid therefrom.

Signed at Berlin, Germany, this" 21st'day of February, 1903.

' EMIL FISCHER. J OSEF VON MERING. -Witnesses:

HENRY Hasraa, WOLDEMAR HAUPT. 

